Patent GB-1280030-A (GB)
Title: A method for producing alternating copolymers
IPC: C08F4/00
Filed: 1969-09-30
Abstract: 1280030 Alternating copolymers SUMITOMO CHEMICAL CO Ltd 30 Sept 1969 [30 Sept 1968] 48031/69 Heading C3P Alternating copolymers in which units derived from type [A] monomers alternate with units derived from type [B] monomers, are produced by contacting at least one type [A] monomer and at least one type [B] monomer with a catalyst system prepared by mixing a catalyst component (a) with a catalyst component (b) in the presence of at least the type [B] monomer, wherein the type [A] monomers comprise: (1) terminally unsaturated olefinic compounds of formula wherein R<SP>1</SP> and R<SP>2</SP> may be the same or different from each other and each represents a hydrogen atom, a halogen atom, a hydrocarbon residue having from 1 to 20 carbon atoms, or a halogencontaining hydrocarbon residue having from 1 to 20 carbon atoms; (2) internally unsaturated olefinic compounds of formula wherein R<SP>3</SP> and R<SP>4</SP> may be the same or different from each other and each represents a hydrocarbon residue having from 1 to 20 carbon atoms, or a halogen-containing hydrocarbon residue having from 1 to 20 carbon atoms; R<SP>5</SP> represents a hydrogen atom, a hydrocarbon residue having from 1 to 20 carbon atoms, or a halogencontaining hydrocarbon residue having from 1 to 20 carbon atoms; and R<SP>6</SP> is a divalent hydrocarbon residue having from 1 to 20 carbon atoms, or a halogen-containing divalent hydrocarbon residue having from 1 to 20 carbon atoms; (3) non-conjugated polyenic hydrocarbons and halogen-containing hydrocarbons having up to 30 carbon atoms and containing at least one carbon-carbon double bond having attached thereto at least 2 hydrogen atoms; (4) acetylenic compounds of formula wherein R<SP>7</SP> represents a hydrogen atom, a hydrocarbon residue having from 1 to 20 carbon atoms, or a halogen-containing hydrocarbon residue having from 1 to 20 carbon atoms; and R<SP>8</SP> represents a hydrogen atom, or a hydrocarbon or halogen-substituted hydrocarbon residue having from 1 to 20 carbon atoms and containing polymerizable unsaturation; and (5) non-conjugated carbonyl- or thiocarbonylcontaining unsaturated compounds of formula wherein R<SP>9</SP> represents a hydrogen atom, a halogen atom, or the group R<SP>12</SP>-, R<SP>12</SP>O-, R<SP>12</SP>S- or R<SP>13</SP>R<SP>14</SP>N-; Z represents an oxygen atom or a sulphur atom; Y repreents an oxygen atom, a sulphur atom or the group -NR<SP>15</SP>-; R<SP>10</SP> represents a hydrocarbon or halogen-substituted hydrocarbon residue having from 2 to 20 carbon atoms and containing polymerizable unsaturation; R<SP>11</SP> represents a divalent organic residue having from 1 to 20 carbon atoms; R<SP>12</SP> represents a hydrocarbon or halogen-substituted hydrocarbon group having from 1 to 20 carbon atoms; and R<SP>13</SP>, R<SP>14</SP> and R<SP>15</SP> may be the same or different from each other and each represents a hydrogen atom, or a hydrocarbon or halogensubstituted hydrocarbon residue having from 1 to 20 carbon atoms; the type [B] monomers comprise conjugated compounds of formula wherein one of R<SP>I</SP> and R<SP>II</SP> represents a hydrogen atom and the other represents a hydrogen atom, a halogen atom, a hydrocarbon residue having from 1 to 20 carbon atoms, or a halogencontaining hydrocarbon residue having from 1 to 20 carbon atoms; and Q represents a nitrile group or a group of formula  wherein Y<SP>1</SP> represents a halogen atom, or the group -Z<SP>1</SP>R, or R<SP>1</SP>; Z<SP>1</SP> represents an oxygen atom or a sulphur atom; R, R<SP>1</SP> and R<SP>11</SP> may be the same or different from each other and each represents a hydrogen atom or an organic residue having from 1 to 20 carbon atoms; R<SP>VII</SP> represents a divalent organic residue having from 1 to 20 carbon atoms; Me represents an ammonium group or an atom of an element from Group I or II of Mendeleev's Periodic Table; and k is equal to the valency of Me; catalyst component (a) is (1) an organo-halide of formula wherein M represents aluminium or boron; R<SP>111</SP> represents a hydrocarbon residue having from 1 to 20 carbon atoms; X represents a halogen atom; and n may have any value from 1 to 2; or a mixture of at least two kinds of compounds having the formulae wherein M, M<SP>1</SP> and M<SP>11</SP> can be the same or different from each other and each represents aluminium or boron; R<SP>111</SP> and R<SP>IV</SP> may be the same or different from each other and each represents a hydrocarbon residue having from 1 to 20 carbon atoms; X and X<SP>1</SP> may be the same or different from each other and each represents a halogen atom; and n may have any value from 1 to 2; or (2) a complex obtained by mixing, in the presence of the type [B] monomer, (i) an organic compound of a metal of Group IIb, IIIb or IVb of Mendeleev's Periodic Table (the term "metal" including boron), and (ii) a compound having at least one metal-halogen bond of a metal from Group IIIb or IVb of Mendeleev's Periodic Table (the term "metal" including boron), at least one of said compounds (i) and (ii) being a compound of aluminium or boron; and catalyst component (b) is a compound of a transition metal from Group IVa, Va, VIa or VIII of Mendeleev's Periodic Table containing at least one halogen atom, alkoxy group, #-diketo group and/or acyloxy group.  Examples describe the production of alternating copolymers of styrene with methyl acrylate, methyl methacrylate, acrylonitrile or acrolein, of methyl acrylate with vinyl acetate, vinyl chloride or acrylonitrile, of acrylonitrile with propylene, isobutylene or norbornene, and of α- methyl styrene with ethyl acrylate, the catalyst systems utilized being ethyl aluminium sesquichloride + vanadyl trichloride, anhydrous chromium, cobalt or nickel chloride, zirconium tetraacetyl acetonate, vanadyl ethoxide dichloride or n-butoxy orthotitanate; diethyl aluminium chloride+vanadium tetraehloride; ethyl boron dichloride+cobalt trisacetylacetonate and triethyl aluminium+tin tetrachloride and cobalt stearate.